WO2018062307A1 - Cellule solaire souple - Google Patents

Cellule solaire souple Download PDF

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Publication number
WO2018062307A1
WO2018062307A1 PCT/JP2017/035025 JP2017035025W WO2018062307A1 WO 2018062307 A1 WO2018062307 A1 WO 2018062307A1 JP 2017035025 W JP2017035025 W JP 2017035025W WO 2018062307 A1 WO2018062307 A1 WO 2018062307A1
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WIPO (PCT)
Prior art keywords
solar cell
photoelectric conversion
aluminum oxide
flexible solar
organic
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PCT/JP2017/035025
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English (en)
Japanese (ja)
Inventor
明伸 早川
麻由美 湯川
智仁 宇野
元彦 浅野
雄一郎 福本
哲也 榑林
哲也 会田
森田　健晴
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積水化学工業株式会社
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Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to BR112019002435-2A priority Critical patent/BR112019002435B1/pt
Priority to EP17856256.7A priority patent/EP3522245B1/fr
Priority to CN201780054740.5A priority patent/CN109690801A/zh
Priority to US16/328,387 priority patent/US20210288277A1/en
Priority to JP2018542665A priority patent/JPWO2018062307A1/ja
Publication of WO2018062307A1 publication Critical patent/WO2018062307A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a flexible solar cell having high durability at high temperature and high humidity and excellent initial performance.
  • a photoelectric conversion element of a solar cell a laminated body in which an N-type semiconductor layer and a P-type semiconductor layer are arranged between opposing electrodes has been actively developed, and silicon or the like is mainly used as the N-type or P-type semiconductor.
  • Inorganic semiconductors are used.
  • a perovskite solar cell using an organic inorganic perovskite compound having a perovskite structure using lead, tin, or the like as a central metal for a photoelectric conversion layer has attracted attention (for example, Patent Document 1 and Non-Patent Document 1).
  • a flexible solar cell has advantages such as ease of transportation and construction due to reduction in thickness and weight, and resistance to impact.
  • a flexible solar cell is manufactured by laminating a photoelectric conversion layer or the like having a function of generating a current when irradiated with light on a flexible substrate in a thin film shape. Furthermore, a solar cell sealing sheet is laminated and sealed on the upper and lower surfaces of the solar cell element as necessary.
  • a flexible solar cell has a problem that the high-temperature and high-humidity durability is inferior when the photoelectric conversion layer contains an organic-inorganic perovskite compound.
  • An object of the present invention is to provide a flexible solar cell having high durability at high temperature and high humidity and excellent initial performance.
  • the present invention is a flexible solar cell having an electrode, a transparent electrode, and a photoelectric conversion layer disposed between the electrode and the transparent electrode on a flexible substrate, wherein the photoelectric conversion layer is organic Including the inorganic perovskite compound, the flexible base material has an aluminum foil and an aluminum oxide film formed on the aluminum foil, and the aluminum oxide film has a total thickness of the aluminum foil and the aluminum oxide film.
  • the flexible solar cell has a thickness ratio of 0.1% to 15%.
  • a metal foil as a flexible base material
  • the cost can be reduced as compared with the case of using a heat resistant polymer, and a high temperature treatment can be performed.
  • an insulating layer is formed on the metal foil in order to insulate the electrode, and this insulating layer generally has a property of easily absorbing moisture. It is often an organic insulating layer.
  • each layer such as an electrode, a photoelectric converting layer, and a transparent electrode, is each patterned so that each cell may be connected in series, an organic insulating layer is also in contact with a photoelectric converting layer. It will be.
  • the photoelectric conversion layer contains an organic / inorganic perovskite compound
  • the moisture in the atmosphere permeates the organic insulating layer and deteriorates the photoelectric conversion layer, so that high temperature and high humidity durability cannot be sufficiently obtained.
  • organic / inorganic perovskite compounds are very sensitive to moisture, perovskite solar cells tend to have a problem of low temperature and high humidity durability compared to other solar cells (for example, CIGS solar cells).
  • the present inventors use an inorganic insulating layer instead of the organic insulating layer, and in particular, use a material having an aluminum foil and an aluminum oxide film formed on the aluminum foil as a flexible substrate.
  • the photoelectric conversion layer contains an organic / inorganic perovskite compound, high high temperature and high humidity durability can be obtained.
  • a flexible solar cell has a problem that the initial photoelectric conversion efficiency may not be sufficiently obtained.
  • the inventors have found that if the aluminum oxide film is too thin or too thick, defects such as poor insulation, poor conduction, and cracks occur, and as a result, sufficient initial performance cannot be obtained. It was.
  • the present inventors suppress the occurrence of these defects by adjusting the ratio of the thickness of the aluminum oxide coating film to the total thickness of the aluminum foil and the aluminum oxide coating film within a specific range, so that a flexible solar cell can be obtained. It was found that the initial performance can be improved, and the present invention has been completed.
  • the flexible solar cell of this invention has an electrode, a transparent electrode, and the photoelectric converting layer arrange
  • the “layer” means not only a layer having a clear boundary but also a layer having a concentration gradient in which contained elements gradually change.
  • the elemental analysis of the layer can be performed, for example, by performing FE-TEM / EDS line analysis measurement of the cross section of the flexible solar cell and confirming the element distribution of the specific element.
  • a layer means not only a flat thin film-like layer but also a layer that can form a complicated and complicated structure together with other layers.
  • the flexible substrate has an aluminum foil and an aluminum oxide film formed on the aluminum foil.
  • the aluminum foil costs can be reduced as compared with the case of using a heat-resistant polymer, and high-temperature treatment can be performed. For example, even when thermal annealing (heat treatment) is performed at a temperature of 80 ° C. or higher for the purpose of imparting light resistance (resistance to photodegradation) when forming a photoelectric conversion layer containing an organic / inorganic perovskite compound, generation of distortion is minimized.
  • a flexible solar cell having high photoelectric conversion efficiency can be obtained.
  • cost can be suppressed compared with the case where other metal foil is used, and workability
  • the photoelectric conversion layer contains an organic / inorganic perovskite compound, high high temperature and high humidity durability can be obtained.
  • the photoelectric conversion layer contains an organic / inorganic perovskite compound by using the flexible base material having the aluminum foil and an aluminum oxide film formed on the aluminum foil, the aluminum foil The phenomenon that discoloration occurs in the photoelectric conversion layer with the passage of time and corrosion occurs can be suppressed. In other general solar cells, it has not been reported that the photoelectric conversion layer reacts with aluminum to cause discoloration, and the phenomenon of corrosion as described above is a problem peculiar to perovskite solar cells. They have found.
  • the crystal structure of aluminum oxide includes a boehmite type that is a monohydrate and a bayerite type that is a trihydrate.
  • the crystal structure of the aluminum oxide in the aluminum oxide film may be a boehmite type. preferable. Since the crystal structure of aluminum oxide in the aluminum oxide film is boehmite, cracks are less likely to occur in the aluminum oxide film at high temperatures.
  • the method for specifying the crystal structure (boehmite type or bayerite type) of aluminum oxide in the aluminum oxide film is not particularly limited.
  • the flexible substrate can be formed using an electron microscope (for example, S-4800, manufactured by HITACHI). A method of observing the surface shape, a method of performing X-ray structural analysis, and the like can be mentioned.
  • FIG. 3 shows an electron micrograph of aluminum oxide having a boehmite type crystal structure
  • FIG. 4 shows an electron micrograph of aluminum oxide having a bayerite type crystal structure.
  • the lower limit of the ratio of the thickness of the aluminum oxide film to the total thickness of the aluminum foil and the aluminum oxide film is 0.1%, and the upper limit is 15%.
  • the ratio is 0.1% or more, the hardness of the aluminum oxide film is increased, and when the electrode is patterned by laser, mechanical scribe, etc., the patterning can be performed satisfactorily and the aluminum oxide film is peeled off. Can be suppressed. Thereby, generation
  • the patterning of the electrode by laser, mechanical scribing or the like is usually performed on the electrode after the electrode is arranged on the aluminum oxide film side of the flexible substrate.
  • the ratio is 15% or less, it is possible to suppress cracking in the aluminum oxide film due to the difference in thermal expansion coefficient from the aluminum foil when heat treatment is performed when forming the photoelectric conversion layer containing the organic / inorganic perovskite compound. can do. Thereby, it can suppress that the crack arises also in the said electrode and the resistance value of a flexible solar cell raises, and the initial stage performance of a flexible solar cell can be improved. Moreover, it can suppress that the said aluminum foil is exposed when a crack arises in the said aluminum oxide film, and corrosion occurs in the said photoelectric converting layer.
  • the preferable lower limit of the ratio is 0.5%, and the preferable upper limit is 5%.
  • the total thickness of the aluminum foil and the aluminum oxide coating is preferably a preferable lower limit of 5 ⁇ m and a preferable upper limit of 500 ⁇ m. If the said total thickness is 5 micrometers or more, it can be set as the flexible solar cell excellent in the handleability which has sufficient mechanical strength. If the said total thickness is 500 micrometers or less, it can be set as the flexible solar cell excellent in flexibility. The minimum with said more preferable total thickness is 10 micrometers, and a more preferable upper limit is 100 micrometers.
  • the preferable lower limit of the thickness of the aluminum oxide film is 0.1 ⁇ m
  • the preferable upper limit is 20 ⁇ m
  • the more preferable lower limit is 0.5 ⁇ m
  • the more preferable upper limit is 10 ⁇ m.
  • the thickness of the aluminum oxide film is 0.5 ⁇ m or more
  • the aluminum oxide film can sufficiently cover the surface of the aluminum foil, and the insulation between the aluminum foil and the electrode is stabilized.
  • the thickness of the aluminum oxide film is 10 ⁇ m or less, the aluminum oxide film is hardly cracked even if the flexible base material is curved.
  • the total thickness of the aluminum foil and the aluminum oxide film, and the thickness of the aluminum oxide film are, for example, by observing a cross section of the flexible substrate with an electron microscope (for example, S-4800, manufactured by HITACHI, etc.) It can be measured by analyzing the contrast of the obtained photograph.
  • an electron microscope for example, S-4800, manufactured by HITACHI, etc.
  • the method for forming the aluminum oxide film is not particularly limited, and examples thereof include a method of forming an aluminum oxide film on the surface of the aluminum foil by anodizing the aluminum foil. Moreover, the method of forming the aluminum oxide film by apply
  • the treatment concentration, the treatment temperature, the current density, the treatment time, etc. are changed. The method of adjusting by doing.
  • the said electrode is arrange
  • Either the electrode or the transparent electrode may be a cathode or an anode.
  • the material of the electrode and the transparent electrode include FTO (fluorine-doped tin oxide), sodium, sodium-potassium alloy, lithium, magnesium, aluminum, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, Al / Examples thereof include Al 2 O 3 mixture, Al / LiF mixture, metal such as gold, CuI and the like.
  • conductive transparent materials such as ITO (indium tin oxide), SnO 2 , AZO (aluminum zinc oxide), IZO (indium zinc oxide), and GZO (gallium zinc oxide), conductive transparent polymers, and the like can be mentioned. It is done. These materials may be used alone or in combination of two or more.
  • the photoelectric conversion layer contains an organic / inorganic perovskite compound.
  • the organic / inorganic perovskite compound is preferably represented by the general formula R—M—X 3 (where R is an organic molecule, M is a metal atom, and X is a halogen atom or a chalcogen atom).
  • the R is an organic molecule, and is preferably represented by C 1 N m H n (l, m, and n are all positive integers). Specifically, R is, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, trimethylamine, triethylamine, tripropyl.
  • ions e.g., 3 NH 3
  • methylamine, ethylamine, propylamine, propylcarboxyamine, butylcarboxyamine, pentylcarboxyamine, formamidinium, guanidine and their ions are preferred, and methylamine, ethylamine, pentylcarboxyamine, formamidinium, guanidine and These ions are more preferred.
  • methylamine, formamidinium, and these ions are more preferable because high photoelectric conversion efficiency can be obtained.
  • M is a metal atom, for example, lead, tin, zinc, titanium, antimony, bismuth, nickel, iron, cobalt, silver, copper, gallium, germanium, magnesium, calcium, indium, aluminum, manganese, chromium, molybdenum, Europium etc. are mentioned.
  • lead or tin is preferable from the viewpoint of overlapping of electron orbits.
  • These metal atoms may be used independently and 2 or more types may be used together.
  • X is a halogen atom or a chalcogen atom, and examples thereof include chlorine, bromine, iodine, sulfur, and selenium. These halogen atoms or chalcogen atoms may be used alone or in combination of two or more. Among these, the halogen atom is preferable because the organic / inorganic perovskite compound becomes soluble in an organic solvent and can be applied to an inexpensive printing method by containing halogen in the structure. Furthermore, iodine is more preferable because the energy band gap of the organic-inorganic perovskite compound becomes narrow.
  • the organic / inorganic perovskite compound preferably has a cubic structure in which a metal atom M is disposed at the body center, an organic molecule R is disposed at each vertex, and a halogen atom or a chalcogen atom X is disposed at the face center.
  • FIG. 1 shows an example of a crystal structure of an organic / inorganic perovskite compound having a cubic structure in which a metal atom M is arranged at the body center, an organic molecule R is arranged at each vertex, and a halogen atom or a chalcogen atom X is arranged at the face center. It is a schematic diagram.
  • the organic / inorganic perovskite compound is preferably a crystalline semiconductor.
  • the crystalline semiconductor means a semiconductor capable of measuring the X-ray scattering intensity distribution and detecting a scattering peak. If the organic / inorganic perovskite compound is a crystalline semiconductor, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the flexible solar cell is improved. In addition, if the organic / inorganic perovskite compound is a crystalline semiconductor, it is easy to suppress the deterioration of photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light to the flexible solar cell, particularly the photodegradation due to the decrease of short-circuit current. Become.
  • the degree of crystallization can be evaluated as an index of crystallization.
  • the degree of crystallinity is determined by separating the crystalline-derived scattering peak detected by the X-ray scattering intensity distribution measurement and the halo derived from the amorphous part by fitting, obtaining the respective intensity integrals, Can be obtained by calculating the ratio.
  • a preferable lower limit of the crystallinity of the organic-inorganic perovskite compound is 30%. If the crystallinity is 30% or more, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the flexible solar cell is improved.
  • the crystallinity when the crystallinity is 30% or more, it is easy to suppress a decrease in photoelectric conversion efficiency (photodegradation) caused by continuing to irradiate light to the flexible solar cell, particularly a photodegradation due to a decrease in short-circuit current.
  • a more preferred lower limit of the crystallinity is 50%, and a more preferred lower limit is 70%.
  • Examples of a method for increasing the crystallinity of the organic / inorganic perovskite compound include thermal annealing (heat treatment), irradiation with intense light such as a laser, and plasma irradiation.
  • the crystallite diameter can also be evaluated as another crystallization index.
  • the crystallite diameter can be calculated by the holder-Wagner method from the half width of the scattering peak derived from the crystal detected by the X-ray scattering intensity distribution measurement. If the crystallite diameter of the organic / inorganic perovskite compound is 5 nm or more, the photoelectric conversion efficiency is lowered (photodegradation) due to continuing to irradiate light on the flexible solar cell, in particular, the photodegradation caused by the short circuit current is suppressed. The In addition, the mobility of electrons in the organic / inorganic perovskite compound is increased, and the photoelectric conversion efficiency of the flexible solar cell is improved. A more preferred lower limit of the crystallite diameter is 10 nm, and a more preferred lower limit is 20 nm.
  • the photoelectric conversion layer may further contain an organic semiconductor or an inorganic semiconductor in addition to the organic / inorganic perovskite compound as long as the effects of the present invention are not impaired.
  • the organic semiconductor include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
  • conductive polymers having a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, and the like can be given.
  • compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, or a benzoporphyrin skeleton, a spirobifluorene skeleton, etc.
  • carbon-containing materials such as carbon nanotubes, graphene, and fullerene that may be surface-modified Also mentioned.
  • the inorganic semiconductor examples include titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, CuSCN, Cu 2 O, CuI, MoO 3 , V 2 O 5 , WO 3 , MoS 2, MoSe 2, Cu 2 S , and the like.
  • the photoelectric conversion layer includes the organic-inorganic perovskite compound and the organic semiconductor or the inorganic semiconductor
  • the photoelectric conversion layer is a laminated body in which a thin-film organic semiconductor or an inorganic semiconductor portion and a thin-film organic-inorganic perovskite compound portion are stacked.
  • a composite film in which an organic semiconductor or inorganic semiconductor part and an organic / inorganic perovskite compound part are combined may be used.
  • a laminated body is preferable in that the production method is simple, and a composite film is preferable in that the charge separation efficiency in the organic semiconductor or the inorganic semiconductor can be improved.
  • the preferable lower limit of the thickness of the thin-film organic / inorganic perovskite compound site is 5 nm, and the preferable upper limit is 5000 nm. If the thickness is 5 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 5000 nm or less, since it can suppress that the area
  • the more preferable lower limit of the thickness is 10 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 20 nm, and the still more preferable upper limit is 500 nm.
  • a preferable lower limit of the thickness of the composite film is 30 nm, and a preferable upper limit is 3000 nm. If the thickness is 30 nm or more, light can be sufficiently absorbed, and the photoelectric conversion efficiency is increased. If the said thickness is 3000 nm or less, since it becomes easy to reach
  • the more preferable lower limit of the thickness is 40 nm, the more preferable upper limit is 2000 nm, the still more preferable lower limit is 50 nm, and the still more preferable upper limit is 1000 nm.
  • the photoelectric conversion layer is preferably subjected to thermal annealing (heat treatment) after the photoelectric conversion layer is formed.
  • thermal annealing heat treatment
  • the degree of crystallinity of the organic-inorganic perovskite compound in the photoelectric conversion layer can be sufficiently increased, and the decrease in photoelectric conversion efficiency (photodegradation) due to continued irradiation with light is further increased. Can be suppressed.
  • the present invention by using the aluminum foil, it is possible to obtain a flexible solar cell having high photoelectric conversion efficiency by minimizing the occurrence of distortion even if thermal annealing (heat treatment) is performed. it can.
  • the temperature for heating the photoelectric conversion layer is not particularly limited, but is preferably 100 ° C. or higher and lower than 200 ° C.
  • the heating temperature is 100 ° C. or higher, the crystallinity of the organic / inorganic perovskite compound can be sufficiently increased. If the said heating temperature is less than 200 degreeC, it can heat-process, without thermally degrading the said organic-inorganic perovskite compound.
  • a more preferable heating temperature is 120 ° C. or higher and 170 ° C. or lower.
  • the heating time is not particularly limited, but is preferably 3 minutes or longer and 2 hours or shorter.
  • the heating time is 3 minutes or longer, the crystallinity of the organic-inorganic perovskite compound can be sufficiently increased. If the heating time is within 2 hours, the organic inorganic perovskite compound can be heat-treated without causing thermal degradation.
  • These heating operations are preferably performed in a vacuum or under an inert gas, and the dew point temperature is preferably 10 ° C or lower, more preferably 7.5 ° C or lower, and further preferably 5 ° C or lower.
  • the flexible solar cell of this invention may have an electron carrying layer between the electrode used as the cathode of the said electrode and the said transparent electrode, and the said photoelectric converting layer.
  • the material of the electron transport layer is not particularly limited.
  • N-type conductive polymer N-type low molecular organic semiconductor, N-type metal oxide, N-type metal sulfide, alkali metal halide, alkali metal, surface activity Agents and the like.
  • Specific examples include cyano group-containing polyphenylene vinylene, boron-containing polymer, bathocuproine, bathophenanthrene, hydroxyquinolinato aluminum, oxadiazole compound, and benzimidazole compound.
  • naphthalene tetracarboxylic acid compound perylene derivative, phosphine oxide compound, phosphine sulfide compound, fluoro group-containing phthalocyanine, titanium oxide, zinc oxide, indium oxide, tin oxide, gallium oxide, tin sulfide, indium sulfide, zinc sulfide, etc. It is done.
  • the electron transport layer may consist of only a thin film electron transport layer (buffer layer), but preferably includes a porous electron transport layer.
  • the photoelectric conversion layer is a composite film in which an organic semiconductor or an inorganic semiconductor site and an organic / inorganic perovskite compound are combined, a more complex composite film (a more complicated structure) is obtained, and the photoelectric conversion efficiency is improved.
  • the composite film is formed on the porous electron transport layer.
  • the preferable lower limit of the thickness of the electron transport layer is 1 nm, and the preferable upper limit is 2000 nm. If the thickness is 1 nm or more, holes can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of electron transport, and photoelectric conversion efficiency will become high.
  • the more preferable lower limit of the thickness of the electron transport layer is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
  • the flexible solar cell of this invention may have a hole transport layer between the said photoelectric converting layer and the electrode used as the anode of the said electrode and the said transparent electrode.
  • the material of the hole transport layer is not particularly limited, and examples thereof include a P-type conductive polymer, a P-type low molecular organic semiconductor, a P-type metal oxide, a P-type metal sulfide, and a surfactant. Examples thereof include compounds having a thiophene skeleton such as poly (3-alkylthiophene).
  • conductive polymers having a triphenylamine skeleton, a polyparaphenylene vinylene skeleton, a polyvinyl carbazole skeleton, a polyaniline skeleton, a polyacetylene skeleton, and the like can be given.
  • compounds having a porphyrin skeleton such as a phthalocyanine skeleton, a naphthalocyanine skeleton, a pentacene skeleton, and a benzoporphyrin skeleton, a spirobifluorene skeleton, and the like can be given.
  • molybdenum oxide, vanadium oxide, tungsten oxide, nickel oxide, copper oxide, tin oxide, molybdenum sulfide, tungsten sulfide, copper sulfide, tin sulfide, etc. fluoro group-containing phosphonic acid, carbonyl group-containing phosphonic acid, CuSCN, CuI, etc.
  • carbon-containing materials such as copper compounds, carbon nanotubes, and graphene.
  • a part of the hole transport layer may be immersed in the photoelectric conversion layer (a structure complicated with the photoelectric conversion layer may be formed) or arranged in a thin film on the photoelectric conversion layer. May be.
  • the thickness when the hole transport layer is in the form of a thin film has a preferred lower limit of 1 nm and a preferred upper limit of 2000 nm. If the thickness is 1 nm or more, electrons can be sufficiently blocked. If the said thickness is 2000 nm or less, it will become difficult to become resistance at the time of hole transport, and a photoelectric conversion efficiency will become high.
  • the more preferable lower limit of the thickness is 3 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 5 nm, and the still more preferable upper limit is 500 nm.
  • the flexible solar cell of the present invention has the electrode, the transparent electrode, and a photoelectric conversion layer disposed between the electrode and the transparent electrode on the flexible substrate as described above, Furthermore, the laminated body which has the said electron carrying layer and the said hole transport layer may be sealed with the sealing material as needed.
  • the sealing material may be sealed with the sealing material as needed.
  • a thermosetting resin, a thermoplastic resin, or an inorganic material etc. are mentioned.
  • thermosetting resin or thermoplastic resin examples include epoxy resin, acrylic resin, silicone resin, phenol resin, melamine resin, urea resin, butyl rubber, polyester, polyurethane, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl alcohol, poly Examples include vinyl acetate, ABS resin, polybutadiene, polyamide, polycarbonate, polyimide, polyisobutylene and the like.
  • a preferable minimum is 100 nm and a preferable upper limit is 100000 nm.
  • a more preferable lower limit of the thickness is 500 nm, a more preferable upper limit is 50000 nm, a still more preferable lower limit is 1000 nm, and a still more preferable upper limit is 20000 nm.
  • the inorganic material examples include Si, Al, Zn, Sn, In, Ti, Mg, Zr, Ni, Ta, W, Cu, or an oxide, nitride, or oxynitride of an alloy containing two or more of these. .
  • oxides, nitrides, or oxynitrides of metal elements containing both metal elements of Zn and Sn are preferable.
  • the said sealing material is an inorganic material
  • a preferable minimum is 30 nm and a preferable upper limit is 3000 nm. If the said thickness is 30 nm or more, the said inorganic layer can have sufficient water vapor
  • the more preferable lower limit of the thickness is 50 nm, the more preferable upper limit is 1000 nm, the still more preferable lower limit is 100 nm, and the still more preferable upper limit is 500 nm.
  • the thickness of the inorganic layer can be measured using an optical interference type film thickness measuring device (for example, FE-3000 manufactured by Otsuka Electronics Co., Ltd.).
  • the method for sealing the laminate with the thermosetting resin or the thermoplastic resin is not particularly limited.
  • the method for sealing the laminate with a sheet-like sealing material or the like Is mentioned.
  • polymerize, the method of making it cool after applying heat to a sealing material, etc. are mentioned.
  • a vacuum deposition method a sputtering method, a gas phase reaction method (CVD), and an ion plating method are preferable as a method of covering the stacked body with the inorganic material.
  • the sputtering method is preferable for forming a dense layer, and the DC magnetron sputtering method is more preferable among the sputtering methods.
  • an inorganic layer made of an inorganic material can be formed by using a metal target and oxygen gas or nitrogen gas as raw materials and depositing the raw material on the laminate to form a film.
  • the sealing material may be a combination of the thermosetting resin or thermoplastic resin and the inorganic material.
  • the sealing material may be covered with another material such as a resin film, a resin film coated with an inorganic material, or a metal foil.
  • the flexible solar cell of the present invention may have a configuration in which the laminate and the other materials are sealed, filled, or bonded with the sealing material. Thereby, even if there is a pinhole in the sealing material, water vapor can be sufficiently blocked, and the durability of the flexible solar cell can be further improved.
  • the flexible solar cell of the present invention is preferably a submodule.
  • the flexible solar cell of the present invention comprises a plurality of cells, and each layer such as the electrode, the electron transport layer, the photoelectric conversion layer, the hole transport layer, and the transparent electrode is connected so that each cell is connected in series. It is preferable to have a patterned structure. Examples of the patterning method for each layer include laser and mechanical scribe.
  • FIG. 2 schematically shows an example of the flexible solar cell of the present invention.
  • the flexible solar cell 1 has an electrode 3, a transparent electrode 4, and a photoelectric conversion layer 5 disposed between these electrodes on a flexible substrate 2.
  • the flexible substrate 2 has an aluminum foil 6 and an aluminum oxide film 7 formed on the aluminum foil 6.
  • the electrode 3, the transparent electrode 4, and the photoelectric conversion layer 5 disposed between these electrodes are respectively patterned.
  • the flexible solar cell 1 has high temperature and high humidity durability even when the photoelectric conversion layer 5 contains an organic-inorganic perovskite compound because the flexible substrate 2 includes the aluminum foil 6 and the aluminum oxide film 7.
  • the ratio of the thickness of the aluminum oxide film 7 to the total thickness of the aluminum foil 6 and the aluminum oxide film 7 is within the above range, the occurrence of defects such as poor insulation, poor conduction, and cracks is suppressed, and the initial performance Will improve.
  • the method for producing the flexible solar cell of the present invention is not particularly limited.
  • positioning the said transparent electrode on the said hole transport layer is mentioned.
  • the method for forming the aluminum oxide film on the aluminum foil when producing the flexible substrate is not particularly limited, but as described above, the surface of the aluminum foil is subjected to anodization by performing anodization on the aluminum foil. A method of forming a film is preferred.
  • Example 1 Anodized aluminum foil An aluminum oxide film was formed on the surface of the aluminum foil by anodizing an aluminum foil (manufactured by UACJ, thickness 100 ⁇ m) by sulfuric acid alumite treatment to obtain a flexible substrate.
  • an electron microscope S-4800, manufactured by HITACHI
  • the thickness of the flexible base material Total thickness
  • the thickness of the aluminum oxide coating were measured. From the measured thickness, the ratio of the thickness of the aluminum oxide film to the total thickness of the aluminum foil and the aluminum oxide film was calculated. Further, the surface of the obtained flexible base material was observed with an electron microscope (S-4800, manufactured by HITACHI), and the crystal structure of aluminum oxide in the aluminum oxide coating was specified to be boehmite type.
  • an electrode made of aluminum having a thickness of 100 nm and a thin-film electron transport layer made of titanium having a thickness of 100 nm are formed by a vapor deposition machine. did. Further, a titanium oxide paste containing polyisobutyl methacrylate as an organic binder and titanium oxide (a mixture of an average particle diameter of 10 nm and 30 nm) is applied onto the thin film electron transport layer by a spin coat method, and then 200 ° C. Was baked for 10 minutes and irradiated with UV for 10 minutes to form a porous electron transport layer having a thickness of 500 nm.
  • lead iodide as a metal halide compound was dissolved in N, N-dimethylformamide (DMF) to prepare a 1M solution, and a film was formed on the porous electron transport layer by a spin coating method. Further, methylammonium iodide as an amine compound was dissolved in 2-propanol to prepare a 1M solution. A layer containing CH 3 NH 3 PbI 3 , which is an organic / inorganic perovskite compound, was formed by immersing the sample formed of lead iodide in the solution. Thereafter, the obtained sample was annealed at 120 ° C. for 30 minutes.
  • a solution was prepared by dissolving 68 mM Spiro-OMeTAD (having a spirobifluorene skeleton), 55 mM t-butylpyridine, and 9 mM bis (trifluoromethylsulfonyl) imide / silver salt in 25 ⁇ L of chlorobenzene.
  • This solution was applied onto the photoelectric conversion layer by a spin coating method to form a hole transport layer having a thickness of 150 nm.
  • an ITO film having a thickness of 100 nm was formed as a transparent electrode by vacuum deposition to obtain a flexible solar cell.
  • Examples 2 to 9 By adjusting the thickness of the aluminum foil used, the treatment time in anodic oxidation, or the treatment temperature, the thickness of the aluminum oxide coating and the ratio thereof were changed as shown in Table 1, and the same as in Example 1, flexible. A solar cell was obtained.
  • Example 3 a flexible solar cell was obtained in the same manner as in Example 1 except that a polyimide resin layer was formed by applying polyimide on the surface of the aluminum foil and baking it.
  • Example 4 A flexible solar cell was obtained in the same manner as in Example 1 except that a PEN film was used instead of the flexible substrate having an aluminum foil and an aluminum oxide coating.
  • Example 5 An ITO film having a thickness of 300 nm was formed on the aluminum oxide film side of the flexible substrate obtained in the same manner as in Example 2 by sputtering. Next, a 50 nm thick polyethylene dioxide thiophene: polystyrene sulfonate (PEDOT: PSS) was used as a hole transport layer to form a film by spin coating on the ITO film. Next, a 4 wt% chlorobenzene solution in which a fullerene derivative (PC60BM) and a conductive polymer (PTB-7) are mixed at a weight ratio of 1: 1 is spin-coated on the obtained hole transport layer, thereby photoelectric conversion. A layer was obtained.
  • PC60BM fullerene derivative
  • PTB-7 conductive polymer
  • an ethanol solution of titanium tetraisopropyl was applied on the obtained photoelectric conversion layer by a spin coating method to form an electron transport layer having a thickness of 10 nm.
  • an ITO film having a thickness of 100 nm was formed as a transparent electrode by vacuum deposition to obtain a flexible solar cell.
  • Submodule performance A submodule of a flexible solar cell was fabricated with the same layer structure as in the example and comparative example.
  • the electrode was divided into six by mechanical scribing. Then, it produced similarly to the Example and the comparative example until the hole transport layer. After forming the hole transport layer, cutting was performed up to the hole transport layer so that the electrode was exposed by mechanical scribing.
  • the transparent electrode is divided into six by mechanical scribing, and patterning is performed so that the six cells are connected in series, thereby obtaining a submodule. It was.
  • a power source (made by KEITHLEY, 236 model) is connected between the electrodes of the submodule of the obtained flexible solar cell, and photoelectric conversion is performed with an exposure area of 9 cm 2 using a solar simulation (manufactured by Yamashita Denso) with an intensity of 100 mW / cm 2. Efficiency was measured. The ratio of the obtained photoelectric conversion efficiency to the initial conversion efficiency obtained in the above (1) was calculated and evaluated as follows.
  • XX 0.6 to less than 0.8 for initial conversion efficiency
  • B 0.4 to less than 0.6 for initial conversion efficiency
  • ⁇ Less than 0.4 for the initial conversion efficiency
  • the value of photoelectric conversion efficiency / initial conversion efficiency after high-temperature and high-humidity durability test is 0.9 or more
  • the value of photoelectric conversion efficiency / initial conversion efficiency after high-temperature and high-humidity durability test is 0.8 or more, 0 Less than 9
  • the value of photoelectric conversion efficiency / initial conversion efficiency after the high-temperature and high-humidity durability test is less than 0.8.

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Abstract

L'objet de la présente invention est de fournir une cellule solaire souple présentant une durabilité à température-humidité élevée et une excellente performance initiale. La présente invention est une cellule solaire souple (1) qui comprend, sur un substrat souple (2), une électrode (3), une électrode transparente (4) et une couche de conversion photoélectrique (5) qui est disposée entre l'électrode (3) et l'électrode transparente (4). Cette cellule solaire souple (1) est conçue de telle sorte que : la couche de conversion photoélectrique (5) contient un composé de pérovskite organique-inorganique; le substrat souple (2) comprend une feuille d'aluminium (6) et un film de revêtement d'oxyde d'aluminium (7) qui est formé sur la feuille d'aluminium (6); et la proportion de l'épaisseur du film de revêtement d'oxyde d'aluminium (7) par rapport à l'épaisseur totale de la feuille d'aluminium (6) et le film de revêtement d'oxyde d'aluminium (7) est de 0,1 % à 15 % (inclus)
PCT/JP2017/035025 2016-09-28 2017-09-27 Cellule solaire souple WO2018062307A1 (fr)

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BR112019002435-2A BR112019002435B1 (pt) 2016-09-28 2017-09-27 Célula solar flexível
EP17856256.7A EP3522245B1 (fr) 2016-09-28 2017-09-27 Cellule solaire souple
CN201780054740.5A CN109690801A (zh) 2016-09-28 2017-09-27 柔性太阳能电池
US16/328,387 US20210288277A1 (en) 2016-09-28 2017-09-27 Flexible solar cell
JP2018542665A JPWO2018062307A1 (ja) 2016-09-28 2017-09-27 フレキシブル太陽電池

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JPS61284971A (ja) * 1985-06-11 1986-12-15 Matsushita Electric Ind Co Ltd 薄膜太陽電池用基板
JP2011108883A (ja) * 2009-11-18 2011-06-02 Mitsubishi Chemicals Corp 太陽電池
JP2011181887A (ja) * 2010-02-08 2011-09-15 Fujifilm Corp 絶縁層付金属基板およびその製造方法、半導体装置およびその製造方法、太陽電池およびその製造方法、電子回路およびその製造方法、ならびに発光素子およびその製造方法
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EP3522245A4 (fr) 2020-05-06
BR112019002435A2 (pt) 2019-06-04
EP3522245B1 (fr) 2022-12-14
US20210288277A1 (en) 2021-09-16
EP3522245A1 (fr) 2019-08-07
JPWO2018062307A1 (ja) 2019-07-11

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